CN115819085B - Preparation method of aqueous phase precursor of high-entropy rare earth diboron carbide nano powder - Google Patents
Preparation method of aqueous phase precursor of high-entropy rare earth diboron carbide nano powder Download PDFInfo
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Abstract
The invention discloses a preparation method of an aqueous phase precursor of high-entropy rare earth diboron carbide nano powder, which comprises the following steps: (1) weighing rare earth salt, boron source and carbon source according to a certain proportion; (2) Adding rare earth salt, boron source and carbon source into distilled water, stirring at room temperature to fully dissolve the rare earth salt, the boron source and the carbon source to obtain a clear solution; (3) Fully drying the clarified solution, and grinding to obtain precursor powder; (4) Hydraulically compacting the precursor powder to obtain a densified blank; (5) And (3) sintering the green body at normal pressure and high temperature under vacuum or protective atmosphere to obtain the high-entropy rare earth diboride nano powder. The high-entropy rare earth diboron carbide nano powder is prepared by a water phase precursor method, so that the high-temperature reduction reaction temperature can be effectively reduced, an organic solvent is avoided, and the low-temperature environment-friendly preparation of the nano powder is realized.
Description
Technical Field
The invention relates to the technical field of high-entropy ceramic materials, in particular to a preparation method of an aqueous phase precursor of high-entropy rare earth diboron carbide nano powder.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
"high entropy ceramics" are new material design theories that have emerged in recent years as a near equimolar multi-component single-phase solid solution ceramic material, whose unique "high entropy effects" can make the material exhibit unique properties in some ways. Rare earth diboron carbide ceramic REB 2 C 2 (RE is rare earth element) has a typical lamellar structure, and the crystal structure of the lamellar structure is composed of RE lamellar layers and B 2 C 2 The rare earth double boron carbide ceramic is formed by alternately stacking in the direction of the c axis, and the diversity of RE position selectable elements lays a good foundation for preparing the high-entropy rare earth double boron carbide ceramic. At present, the prior reports mainly research the single component YB 2 C 2 The related performance of the ceramic shows that YB 2 C 2 The ceramic has high melting point, high strength and excellent damage capacityLimited processability, good high-temperature stability and the like, and has wide application prospect in the fields of aerospace, national defense, military industry and the like.
The solid phase method is a method commonly adopted for preparing the rare earth diboron carbide ceramic and mainly comprises an elemental method and a high-temperature reduction reaction method. The elemental method is a method for synthesizing ceramics by directly carrying out chemical combination reaction on simple substance powder serving as a raw material at high temperature, but the use of the method is limited by the high price of the rare earth simple substance powder. The high-temperature reduction reaction method comprises carbothermic reduction method and boron/carbothermic reduction method, which are oxide and C, B, B 4 The method for synthesizing ceramic powder by using reducing agents such as C and the like as raw materials through reduction reaction at high temperature. In order to improve the purity of the powder, the high-temperature reduction reaction must be sufficiently carried out, so that the synthesized rare earth diboron carbide ceramic often needs to be kept at a temperature of more than 1800 ℃ for a certain period of time, but long-time high-temperature treatment can cause grain growth, so that the nano powder is difficult to prepare, and the sintering activity of the powder is reduced.
Aiming at the problems of the solid-phase method for preparing the rare earth diboride ceramic, a novel preparation method of the high-entropy rare earth diboride nano powder is needed to be explored so as to solve the problems of high reaction temperature, large size of the obtained powder, poor sintering activity and the like of the solid-phase high-temperature reduction reaction method.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the method for preparing the aqueous phase precursor of the high-entropy rare earth diboron carbide nano powder, which prepares the nano powder by the aqueous phase precursor method, can avoid the use of organic solvents and realizes the low-temperature environment-friendly preparation of the nano powder.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing an aqueous phase precursor of high entropy rare earth diboron carbide nano powder, comprising the steps of:
(1) Weighing rare earth salt, boron source and carbon source according to a certain proportion;
(2) Adding rare earth salt, boron source and carbon source into distilled water, stirring at room temperature to fully dissolve the rare earth salt, the boron source and the carbon source to obtain a clear solution;
(3) Fully drying the clarified solution, and grinding to obtain precursor powder;
(4) Hydraulically compacting the precursor powder to obtain a densified blank;
(5) And (3) sintering the green body at normal pressure and high temperature under vacuum or protective atmosphere to obtain the high-entropy rare earth diboride nano powder.
Preferably, the rare earth salt is hydrochloride, nitrate or acetate corresponding to rare earth elements, the rare earth elements are selected from scandium, yttrium and lanthanide elements, and the molar ratio of each rare earth element is 1.
Preferably, the boron source is boron oxide or boric acid, and the carbon source is sucrose or glucose.
Preferably, in the step (1), the rare earth salt, the boron source and the carbon source are respectively weighed according to the molar ratio of the sum of rare earth metals, the boron element in the boron source and the carbon element in the carbon source of 1:5-7:16-18.
Preferably, in the step (3), the clear solution is dried at 90-200 ℃ for 20-48 hours.
Preferably, in the step (4), the hydraulic compaction pressure is 150-300 MPa, and the dwell time is 5-15 min.
Preferably, in step (5), the selected protective atmosphere is argon or helium.
Preferably, in the step (5), the sintering treatment is heated to 1700-2000 ℃ at a heating rate of 5-20 ℃/min, and the heating is stopped after the heat preservation is carried out for 1-5 hours, so that the sintering treatment is cooled to the room temperature along with the furnace.
Preferably, in the step (5), the sintering treatment is heated to 1750-1850 ℃ at a heating rate of 10 ℃/min, and the heating is stopped after the heat preservation is carried out for 1-2 hours, so that the sintering treatment is cooled to room temperature along with the furnace.
In a second aspect of the invention, there is provided a high entropy rare earth diboron carbide nanopowder prepared from the aqueous phase precursor preparation method of the first aspect.
One or more of the technical schemes of the invention has the following beneficial effects:
(1) The invention adopts the aqueous phase precursor method to prepare the high-entropy rare earth diboron carbide nano powder, realizes the molecular level mixing of reactants under the liquid state environment, shortens the high-temperature reduction reaction path, effectively reduces the high-temperature reduction reaction temperature, can prepare the nano powder by adopting a simple process, and solves the problems of high reaction temperature, large size of the obtained powder, poor sintering activity and the like in the solid phase high-temperature reduction reaction method.
(2) The synthetic route of the aqueous phase precursor provided by the invention can avoid the use of an organic solvent and realize the low-temperature environment-friendly preparation of the high-entropy rare earth diboron carbide nano powder.
Drawings
FIG. 1 shows the process of the present invention (Y) 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 XRD pattern of nano powder;
FIG. 2 shows the process of example 1 (Y 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 And (3) a transmission electron microscope morphology graph of the nano powder.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
Aiming at the problems of a solid-phase high-temperature reduction reaction method, the invention provides a method for preparing an aqueous phase precursor of high-entropy rare earth diboron carbide nano powder, which takes water-soluble rare earth salt, a carbon source and a boron source as raw materials, realizes the molecular-level mixing of reactants in an aqueous solution, shortens a high-temperature reduction reaction path, reduces the high-temperature reduction reaction temperature, can avoid using an organic solvent, and realizes the low-temperature environment-friendly preparation of the nano powder.
Example 1
(1) Weighing 10g of yttrium chloride, samarium chloride, gadolinium chloride, holmium chloride, erbium chloride, boron oxide and sucrose according to the element molar ratio Y, wherein Sm, gd, ho and Er are respectively C=1:1:1:1:30:84;
(2) Adding the above materials into 70mL distilled water, stirring at room temperature for 24h to fully dissolve to obtain a clear solution;
(3) Drying the clarified solution at 150 ℃ for 24 hours, and grinding after fully drying to obtain precursor powder;
(4) Compacting the precursor powder by hydraulic pressure (the holding pressure is 200MPa and the holding time is 10 min) to obtain a densified blank;
(5) Placing the blank into a graphite crucible, placing the graphite crucible into a multifunctional sintering furnace, heating to 1800 ℃ at 10 ℃/min under argon atmosphere, preserving heat for 1h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 Nano powder.
FIG. 1 shows the XRD pattern of the nano powder prepared in example 1, and as can be seen from FIG. 1, the obtained product is a pure single-phase solid solution.
Fig. 2 is a transmission electron microscope morphology diagram of the nano powder prepared in example 1, and it can be seen from fig. 2 that the size of the obtained powder is nano-scale.
Example 2
(1) Weighing 10g of yttrium chloride, ytterbium chloride, gadolinium chloride, dysprosium chloride, erbium chloride, boron oxide and glucose according to the element molar ratio Y, gd, dy, er and C=1:1:1:1:28:83;
(2) Adding the above materials into 60mL distilled water, stirring at room temperature for 20h to fully dissolve the materials to obtain a clear solution;
(3) Drying the clarified solution at 140 ℃ for 24 hours, and grinding after fully drying to obtain precursor powder;
(4) Compacting the precursor powder by hydraulic pressure (the holding pressure is 200MPa and the holding time is 10 min) to obtain a densified blank;
(5) Placing the blank into a graphite crucible, placing the graphite crucible into a multifunctional sintering furnace, heating to 1800 ℃ at 10 ℃/min under argon atmosphere, preserving heat for 1h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Yb 0.2 Gd 0.2 Dy 0.2 Er 0.2 )B 2 C 2 Nano powder.
Example 3
(1) Weighing 20g of yttrium chloride, cerium chloride, gadolinium chloride, dysprosium chloride, erbium chloride, boric acid and sucrose according to the element mole ratio Y, ce, dy, er and C=1:1:1:1:30:84;
(2) Adding the above materials into 120mL distilled water, stirring at room temperature for 24h to fully dissolve the materials to obtain a clear solution;
(3) Drying the clarified solution at 180 ℃ for 30 hours, and grinding after fully drying to obtain precursor powder;
(4) Compacting the precursor powder by hydraulic pressure (the holding pressure is 180MPa, and the holding time is 10 min) to obtain a densified blank;
(5) Placing the blank in a graphite crucible, placing the graphite crucible in a multifunctional sintering furnace, heating to 1850 ℃ at 5 ℃/min under argon atmosphere, keeping the temperature for 2 hours, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Ce 0.2 Gd 0.2 Dy 0.2 Er 0.2 )B 2 C 2 Nano powder.
Example 4
(1) 15g of yttrium nitrate, samarium nitrate, gadolinium nitrate, holmium nitrate, erbium nitrate, boron oxide and sucrose are weighed according to the element mole ratio Y, sm, gd, ho and Er, B and C=1:1:1:1:1:30:84;
(2) Adding the above materials into 100mL distilled water, stirring at room temperature for 24h to fully dissolve to obtain a clear solution;
(3) Drying the clarified solution at 200 ℃ for 20 hours, and grinding after fully drying to obtain precursor powder;
(4) Compacting the precursor powder by hydraulic pressure (the holding pressure is 200MPa and the holding time is 10 min) to obtain a densified blank;
(5) Placing the blank into a graphite crucible, placing the graphite crucible into a multifunctional sintering furnace, heating to 1800 ℃ at 10 ℃/min under argon atmosphere, preserving heat for 1h, stopping heating, and cooling to room temperature along with the furnace to obtain (Y) 0.2 Sm 0.2 Gd 0.2 Ho 0.2 Er 0.2 )B 2 C 2 Nano powder.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (4)
1. The preparation method of the aqueous phase precursor of the high-entropy rare earth diboron carbide nano powder is characterized by comprising the following steps:
(1) Weighing rare earth salt, boron source and carbon source according to a certain proportion;
(2) Adding rare earth salt, boron source and carbon source into distilled water, stirring at room temperature to fully dissolve the rare earth salt, the boron source and the carbon source to obtain a clear solution; the rare earth salt is water-soluble rare earth salt;
(3) Fully drying the clarified solution, and grinding to obtain precursor powder;
(4) Hydraulically compacting the precursor powder to obtain a densified blank; the hydraulic compaction pressure is 150-300 MPa, and the pressure maintaining time is 5-15 min;
(5) Sintering the green body at normal pressure and high temperature under vacuum or protective atmosphere to obtain high-entropy rare earth diboron carbide nano powder; heating to 1750-1850 ℃ at a heating rate of 10 ℃/min in sintering treatment, and stopping heating after heat preservation for 1-2 h, so that the material is cooled to room temperature along with a furnace;
the rare earth salt is hydrochloride, nitrate or acetate corresponding to rare earth elements, the rare earth elements are selected from scandium, yttrium and lanthanoid elements, and the molar ratio of the rare earth elements is 1;
the boron source is boron oxide or boric acid, and the carbon source is sucrose or glucose;
in the step (1), the rare earth salt, the boron source and the carbon source are respectively weighed according to the molar ratio of the boron element in the rare earth metal sum to the carbon element in the carbon source of 1:5-7:16-18.
2. The method for preparing the aqueous phase precursor of the high-entropy rare earth diboron carbide nano powder according to claim 1, wherein in the step (3), the drying temperature of the clarified solution is 90-200 ℃ and the drying time is 20-48 h.
3. The method for preparing the aqueous phase precursor of the high-entropy rare earth diboride nano powder according to claim 1, wherein in the step (5), the selected protective atmosphere is argon or helium.
4. The high-entropy rare earth diboron carbide nano powder is characterized in that: a process for preparing an aqueous phase precursor according to any one of claims 1 to 3.
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